Process and apparatus for manufacture of asphaltic products



April 3, 1934. E. w. GARD UAL PROCESS AND APPARATUS FOR MANUFACTURE OF AS PHALT IAC PRODUC Filed July 22. 1929 Patented Apr. 3, 1934 UNITED STATES PROCESS AND APPARATUS FOR MANU- FACTURE F ASPHALTIC PRODUCTS Earle W. Gara, Palos verdes Estates, ana Blair G.

Aldridge, Long Beach, lalif.

Application July 22, i929, Serial No. 380,055

l' Claims.

This invention relates t a process and apparatus for treating petroleum oils, and in particular to the production of oxidized or air-blown The use of air and steam in varying proportions has been used for many years and is well known in the art of producing oxidized asphalt. By varying the proportions of, air and steam, the quality of the asphalt may be changed slight,

l() ly. The time required to blow down the petroleum oil to the required specication varies from 18 to 3 6 hours, depending upon the character of the original stock and the character of the final product. Generally, the higher the A. P. I. gravity 13 of the charging stock, the longer the time required for the process to bring ,the stock tothe desired characteristics. f

In the processes now in use it is impossible to obtain a high melting point asphalt, 250 F. and

i) above, with a penetration of over 15 and a ductility of over l cm. at 77 F. The melting point, penetration and ductility, are not independently variable. If the melting point is increased, the penetration is decreased and the ductility de- 23 creased. This is due to the fact that the meth-f^ ods used cause some of the` asphalt to become over-oxidized and part to be under-oxidized. This isv due to the fact that certain of the constituents are more refractory, i. e., oxidize slower than :3 others. The air passes through the oil in large globules and is not mixed intimately with all of the oil. `The rate of oxidation must be fairly slow or the temperature of the oil will rise .too high, with a resultant low yield and poor qual- A 25 ity of asphalt. In processes where oil is mixed with air in a tube, the rate of oxidation is not controlled, and consequently the oxidation is not uniform and the same evils result.

It is an object of our invention to control the 3 melting point, penetration and ductility so as to vary them independently, and it will make asphalts of any desired specifications.

It i's a; further object of our invention to control Vthe oxidation ofthe oil to produce asphalt 1 3 so as to obtain a uniformly evenly oxidized oil, the varying components of which will not become over-oxidized or under-oxidized. y

It is a further object of our invention to provide a process and apparatus for controlling the 3 intermingling of the oil and oxygen, to regulate --the rate of reaction, and to control the character of the oxidation. n

It is afurther object of our inventicfn to estabv lish an equilibrium relationship between the oil J0 to be oxidized and the oxygen-containing gas,

(Gil. 1196-74) whereby maximum emciency of oxidation is obtained, and to remove the gaseous and vaporous reaction products from the system so that engen at optimum concentrations may act on the oli in process. 6,0

It is a further object of our'invention to conn trol the oxidation of the oil so as to partially oxidize the oil by contacting it with oxygen-containing gas to produce substantially complete use of the air under controlled conditions and to remove the gaseous and vaporous reaction products andto repeat this partial oxidation in recurring cycle of operation until products of desired char acteristics are obtained.

It is a further object of our invention to con 70 trol the temperature of the reacting products.

i.' e., the oil and air, so as to maintain the re acting products at a controlled temperature dur= ing reaction.

lIt is a further object of our invention to cause 75 the intimate commingling of the oil and air lor a predetermined length of time under controlled temperature and to separate the Vaporous and gaseous products and to repeat the process'in recurring cycles of operation until a product of desired quality is obtained.

Other objects will appear from the description of the preferred embodiment of our process appearing below.

We have found that in order to obtain asphalts of high melting point which will have high ductility and desired penetration, it is necessary to produce an intimate mixture of the oil to be oxidized and the4 oxygen-containing gas, such as air, so that all parts of the oil are simultaneously exposed to the ,action of the air. It is also de= srable to maintain the air in intimate contact with the oil so that the oxygen of the air is consumecl as much as possible. This promotes emciency in the use of air andalso permits the more refractory components of the oil to be oxidized. These components need incre time, since they oxidize much slower. During this reaction an increase in the temperature occurs, and prem vision should be made to control the temperature to prevent over-oxidation. This, it will be found,v necessitates, under most circumstances, an ab' straction oi.6 heat, except when very hard asphalts are desired, heat may be added. It is recognized that in the methods nov;r employed, where air is blown through the oil, that some cooling by con tact with the cold air necessarily results. But this incidental and uncontrolled cooling' is far re moved from the present controlled cooling. Aciditionally, in orderto get any amount of cooling no so much excess air must be used as to result in over-oxidation and uncontrolled oxidation and a rise in temperature due to oxidation which counterbalances the cooling effect and actually heats the oil. 'Ihe final effect of the air is to actually heat the oil, for in every case the heat of oxidation more than offsets the cooling effect of the injected cold air. We have also found that the products of the reaction should be removed so that the partially oxidized components may be again contacted with -fresh 'I'he process and -apparatus will be better understood-vv by reference to the drawing which contains a more or less schematic embodiment of 'the apparatus. Fig. 1 is` a flow view of the apparatus with parts broken away. Fig. 2 is a cross-sectional view taken along lline B-B on Fig. 1. 1 is a cylindrical still for containing the bulk supply of oil.

4 is a valve .connecting charging line 2 with the d internal charging line 3 for charging still 1.

5 is ak second charging line and 6 a valve in lines. 7 is ajet mixer in which the oil and air or steam are intimately mixed before being passed through exchanger 9.

8 is an equilibrium onduitin which the` oxidation of the oil takes place.

9 is an exchanger of which the equilibriunn conduit is a part and is used for cooling or heatingthe oil during its passage therethrough.

10 is a return pipe extending through the shell of the still 1 connecting conduit 8 with still 1.

` 11 is a separating pan over which the oil passingfrom 10 is distributed so that vapors and air can be released.

12 is a baille plate in stll'l` extending across the bottom vof the still to form two compartments in the bottom of the still.

pump 14 extending to driving pump 14.

17 is a dischargeline from pump 14 to mixer 7.

18 is a section of pipe connected to valve 19 for admitting air or steam into mixer 7.

20 is a section of pipe connected to valve 21 for transmitting heating and cooling media to or from equilibrium conduit 8 and exchanger 9.

23 is a section oLpipe connected to valve 22 i'or transmitting heating and cooling media, such as steam, oil or air, to or from exchanger 9 and equilibrium conduit 8. It is obvious that instead of using a jacketed pipe any other type of cooling coil may be employed as, for instance,an aerial cooler including 'means for regulating the ow of air over the coil 8. i

34 is a discharge pipe containing valve 33 to be used in discharging oil from still 1 to storage.-

24 are pipe sectionscontaining clean-out plugs 241 and used to connect the vapor lines 27 and 26 and to the shell of still 1.

28 is a section of pipe connected to vapor line 27 to lead the vapors away from still'1.

29 is a slide valve positioned in the extreme b ot- 'tom of bailleplate 12 to allow oil to now from through 'pump 14 and line 13 into still 1.'

24u are Ts used to connect sections of vapor line 27 together.

25 are 'sections of pipe connecting vapor crosses 24 to vapor pipes 26 and 27. p

35 is a valve in. steam agitation spider 37 connected to steam supply line 39. l

38 is4 a valve positioned between pipe 10 and equilibrium conduit 8 which is to be closed when discharging oil through valve 33 and pipe 34.

40 is a section of pipe connected to valve 41, which is.. in turn, connected to the bottom of still 1 and is to be used as a pump-out or drain line.

42 is a valve in bottom agitation spider 43.

44 is connected to steam and air supply lines.

36 are electric leads to motor 15.

45 is the heater or iirebox positioned under st ill 1 for supplying external heat tothe still..

46 is a burner for supplying heat to the heater or nrebox 45.

47 is a manhole for cleaning the still. A hydrocarbon oil, or preferably a residuum from such an oil obtained by distilling off the volatile oils fromcrude oil, is charged into line 5, through valve 6 and mixer 7 and line 17, then The oil mayalso be charged directly to the still 1 through line 3 and valve 4 or-through the discharge line 34 valve 33, valve 38 and line 10, into still 1. Preferably, the oil is charged backward through pump 14, valves 33, 38, 42, 41, 35 and 19 being closed. When the required charge is in the still, pump 14 driven by shaft 16 and motor 15 connected to an electrical'circuit through lines 36 is started and the oil in still 1 is forced through line 17 mixer 7, then through equilibrium conduit 8 of exchanger 9, where it is heated by any heating medium, such as steam or hot oil, entering line 20 and valve 21 and exiting through valve 22 and line 23,- valve 38 being open. The oil then flows through line 10 onto separating pan 11 and back into still 1. Slide valve 29, located in baille plate 12 and operated by connecting link 30 connected to handle 31 which is supported byqfulcrum 32 attached to shell of still-1, is opened during the heating-up period. The fire under still 1 is lighted and the oil is additionally heated by the gases of combustion in irebox 45. The oil is circulated and additional material is introduced through valve 6. As soon as therequired amount of oil, about 300 barrels is charged-to the still, valve 6 is closed andabout 200 cu. ft. of air/minute is admitted through valve 19 and line 18'into mixer 7. The oil is now circulating at the rate vof between 1500 and 2000 bbL/hr. by pump 14. This rate of airv admission is continued until the oilin the still 1 reaches a temperatureof around 300 F. This should require about one hour. The air is then increased to 300 cu. ft./min. and continued at this rate until the oil reaches a temperature of 500 F. This should require about four hours. A 4small amount of top steam is put in through line 39, valve 35 and upper agitation spider 37, as soon as the oil reaches 300 F. The amount of steam is varied, depending upon the specifications to be met, as will be described below. The vapors and steam leave the still through vaporI line 28 and connections 26 and 27. Slide valve 29A run toiaugment circulation in the still, and it is generally increased after the oil reaches 500 F. 'I'his steam distillati-on is used at this stage to control the flash of the stockL as will be described below. This may require one hour. The rate of circulation of the oil through exchanger 9and equilibrium conduit 8 may be controlled'by valve 38or by Varying the speed of the pump 14 through shaft 16 and motor 15. The cooling medium, such as steam, oil or air, in exchanger 9, may be circulated at any desiredl amount to obtain the proper amount of cooling by heat exchange out of contact with the reacting materials. When the oil has been brought down to desired grade it may be left in the still until needed or pumped or drained out through line 40, and valve 41, or it may be pumped out by pump 14 through the discharge line 34 and valve 33 after valve 38, valve 19 and valve 6 have been closed. In either method of removing the oil, slide valve 29 must be opened so that` all of the oil can be removed.

We prefer touse a slight vacuum in the vapor line and stillabout 5 ins. waterto facilitate the removal of the gases.

As a specific examplefwe will describe the'operation and the type of oil. An asphaltic residuum, obtained by removing the light oils and intermediate boiling oils from our asphaltic base oil, is charged, through a preheater (not shown) into a still through a jet-like mixer 7 as previously described abov'e. As soon as the oil is in the still the circulating pump is started'and the oil is circulated at a high rate through the exchanger and back into the still. The heating medium is passed through the exchanger and the still is fired until the oil reaches 500 F. Air is forced or drawn into the oil just before it enters the exchanger and equilibrium conduit. The amount of air is regulated so that the oil rises in temperature to about 500 F. As an example,oil circulated by the pump at 1500 to 2000 bbl./hr.; air is admitted at the rateof 200 cu. ft. per minute until the oil reaches 300 F. The air is then increased to 300 cu. ft. per minute until the oil has attained a maximum of 500 F. As soon as the oil reaches this temperature, the fire is put outunder the still and` sufficient cooling medium is vcirculated in the exchanger and equilibrium conduit to keep the temperature. of the oil being processed below 500 F'.

Hot or cold water, or oil or steam. of controlled pressure and temperature or air may be used to control the temperature in the conduit. The length of pipe in the exchanger and equilibrium conduit and the circulation of oil and the, air input is such that the oxygen of the air is substantially used up before the oil is returned to the still where the air and gases and light vapors are removed.

Ihe oil is circulated very rapidlyl and thus all parts of the oil are kept in intimate contact with the air at practically all times. We have discovered that generally a low temperature should be4 used in such processes, so that a. superior product may be produced. ,This temperature should be as far below 500 F. as it is possible to carry it.

"f If the temperature be raised to too high a degree,

considerable distillation of the lighter fractions will take place and the stock will attain the proper penetration before the desired melting point is reached. This -is due to the removal ofthe light fractions 'which oxidize to a more plastic material By using the equilibriumconduit a. minimumof air is used, so that we are able to use about half the amount now used in the other processes. We have also discovered that by using rapid circulation and the controlled amount of air and the carefully regulated temperature in the exchanger and equilibrium conduit, the running time is reduced to half that now regularly required in the other systems.

Steam may be admitted during the process through agitation'spider 43. This aids to insure circulation of the oil in the still and in obtaining the right flash -point for the product. Steam may also be admitted, either throughout or toward the end of the process, through spider 37 to aid in obtaining the proper flash and ductility. This will be understood by those skilled in the art. The vapors and gases are withdrawn through line 28 as previously described, preferably under light suction. v

Steam may also be admitted through line 19 together Withair so as to control the rate of oxidation and also to control the ductility and flash. It' will be observed that the apparatus can be also very effectively used as a process for making steam-blown asphalt. In this case no air is ad- A. mitted and a heating medium is circulated through blown asphalt and of importance also in steam distillation.

It will be observed that many variations of the above procedure .can be made without departing from the spirit of the invention. Thus, the cooling can be obtained by cooling the oil in the still 1 byI passing the cooling medium through a coil in the still. The agitation of the oil in the still may be by circulation by a mechanical means, or by injection of an inert gas, or by the airA used in the process. The conduit can be positioned either within the still or in an external heating zone, such as a furnace, or the oil may be withdrawn from the still,passed through a cooler and then sent through the conduit 8 before it is intro-I duced into the still. In each case the'oil in conduit 8. on its reaction with air, is not allowed to exceed a predetermined temperature. While the precooling of the oil before introduction of the oil into conduit 8 may have some advantages, the cooling of the oil during reaction with the air is preferred. hIt is believed that of these methods for accomplishing this, i. e. cooling the coil itself or cooling the oil in still 1 when the coil 8 is immerseddn still 1, the former is preferred. It is believed that the construction illustrated in the drawing is the most advantageous.

We have discovered that by properly controlling the heat-air-steam, time and rate of circulation,

a wide variation of melting point. penetration and' and control, the ductility can be raised considerably higher.

We have found that/we can produce a new mal' terial whichis an oxidized asphalt that is evenly` oxidized and does not contain large proportions of over-oxid'zed or under-oxid'zed material.Y

The process lis more economical to operate than any other. We have. been able to use approximately 50% or less air than in the present systems. We have been able to reduce the time approximately 50% or more. By operation,

according to our invention, the yield of oxidized asphalt is increased. We have been able to pro- 5 duce any grade of oxidized material by an even control of air-steam-heat and rate of circulation,v and. to produce an oxidized material with the production of practically no carbon in the still.

Whenever melting point is mentioned, it is to be interpreted as measured by the A. S. T. M. method D-36-24, also disclosed in the Kansas City Testing Laboratory Bulletin No.; 25, page '641. Whenever penetration is mentioned, it is to be interpreted as measured by the A. S. T. M. method D-5-25, also described in the Kansas City Testing Laboratory Bulletin No. 25, pages 686 and 687. Whenever ductility is-mentioned, itl is to be interpreted as measured by the A. S. T. M. method D-113--26T, also described in the Kansas City Testiag Laboratory Bulletin No. 25, page 688.

We claimf 1. A method of producing asphalt which comprises intimately commingling oxidizing gas and 25 oil at an elevated oxidizing temperature in an elongated conduit, controlling the temperature or said oil and gas by passing a heat absorbing -medium in heat exchange relationship with oil in said conduit to absorb heat therefrom.

2. `A method of producing asphalt which comprises passing oil and air through an elongated conduit, passing a cooling medium in heat exchange relationship with the oil in said conduit and separating the oil at an ,elevated oxidizing temperature from the residual air.

3. A method of producing asphalt which comprises circulating oil from a bulk supply through .an elongated conduit back to said bulk supply, intimately commingling oil at an elevated oxidizgas into-said conduit, withdrawing vapors and gas from said bulk supply and controlling thereaction so as to insure substantially complete consumption of the oxygen Yin said conduit.

4. A-method of producing asphalt .which co prises circulating oil from a bulk supply throuli an elongated conduit back to said bulk supply, intimately commingling oil at an elevated oxidizing temperature and free oxygen-containing gas `into said conduit and withdrawing vapors and gas fromsaid bulk supply, regulating the temperature of said oil in said bulk` supply by cooling the oil in said conduit.

5. In combination, a drum, a pump, a suctionv pipe connected to the drum and to the suction side ofthe pump, a return conduit connected to the drum' and to the discharge side of the pump, a baille positioned in said drum between said suction pipe and said return conduit, a valved orice in saidbaiile.

6. A method of oxidizing oil which comprises passing oil at an elevated oxidizing temperature.

and air through an elongated conduit, passing a cooling medium in heat exchange relationship with the oil in said conduit and separating the oil from the residual air.

7. A method of oxidizing oil whichfcomprises circulating oil from a bulk supply through an elongated conduit back to said bulk supply,I intimately commingling oil t an elevated oxidizing temperature and free oxygen-containing gas into said conduitv and withdrawing vapors andgas from said bulk supply, regulating the temperature of said oil in said bulk supply by cooling the oil in said conduit.

running ing temperature and a free oxygen containing` 8. Method-of producing asphalt which comprises, commingling oil atan elevated oxidizing temperature and air, passing said commingled oil and air through an elongated conduit', and introducingsaid commingled oil and air intoa separating chamber, separating the vapors and y gases from saidv oil, passing a cooling medium in heat exchange relationship with the oil and air owing through said elongated conduit.

9. A method of oxidizing oilto produce asphalt.

which comprises intimately commingling an oxidizing gas and oil at an elevated asphalt forming temperature, regulating the temperature of the oil to maintain said oil-gas mixture not above Y said oil at an elevated'asphalt forming ytemperature, regulating the temperature of the oil to maintain said oil not above a predetermined temperature by passing a fluid medium lat a temperature lower than saidkcirculating oil gas mixture in heat exchange with-said oil gas mixture to cool the circulating oil undergoing oxidation, and removing the oxidized asphalt.

11. A method of oxidizing oil to produce asphalt which comprises maintaining an oil at an elevated asphalt oxidizing temperature in a bulk supply, withdrawing oil from said buik supply and passing it in a restricted stream back to said bulk supply,- intimately commingling air with said oil in said restricted stream, cooling said oil in the circulated stream andcontinuing. the process to produce oxidized asphalt, and removing oxidized asphaltirom said bulk supply.

-12. 'A method of oxidizing oil toproduce asphalt-which comprises intimately commingling an oxidizing gasand oil at an elevated asphalt 'forming temperature to form oxidized asphalt. passing a cooling medium in controlled amounts in indirect heat exchange with said oil-gas mixture and removingA oxidized asphalt.

inc

13. A method of oxidizing oil to produce as-4 phalt which comprises maintaining oil in bulk ,L

supply at an elevated asphalt forming temperature, circulating a. stream of said oil, commingling an oxidizing'gas with said stream of oil, passing a cooling medium in controlled amounts in indirect heat exchange with said c'rculating oil and removing oxidized asphalt from said bulk supply. 14. A method of producing oxidized asphalt which comprises maintaining a body of oil in a` still at an elevated asphalt forming temperature, pumping said oil from said bulk supply back into said bulk supply in a circulating stream, intimately commingling air with said circulating stream of oil and passing a cooling medium in controlled amounts in indirect heat exchange with said oil and gas mixture and removing oxidized asphalt.

15. ,A method of producing oxidized asphalt which comprises maintaining a. body of oil in a still in an"elevated asphalt forming temperature, circulatinga restricted stream of oil from said still back to the bodyof oil in said still, introducing air into the circulated restrictedA stream .causing an intimate mixture of said oil and gas in saidrestricted stream, cooling said oil in said restricted stream `by passing a cooling means in viso indirect heat exchange relationship with. said oil and gas mixture, continuing said circulation to produce oxidized asphalt and removing oxidized asphalt from said still.

16. A method of producing oxidized asphalt which comprises maintaining a bulk supply of asphaltic oil at an elevated asphalt forming temperature in a still, circulating the oil from said bulk supply through a mixer and returning the circulating oil to the bulk supply, commingling air and oil in said mixer and cooling the oil by passing a cooling medium in controlled amounts in indirect heat exchange relationship with said oil, continuing said circulation to produce oxidized asphalt, and removing oxidized asphalt from the still.

17. A method for oxidizing oil to produce asphalt which comprises withdrawing oil maintained vat an elevated asphalt forming temperature from a bulk supply, passing said circulating oil through an elongated conduit and introducing said oil back into said bulk supply, intimately commingling said circulating oil with an oxidizing gas, cooling said oil while circulating through lation to produce oxidized asphalt and withdrawing oxidized asphalt.

v EARLE W. GARD.

BLAIRI G. ALDRIDGE.

85. the elongated conduit and continuing said circui i 

